Primary diazo dye derived from diamino carbazoles and arylides of unsulphonated hydroxy carboxylic acid



Patented Mar. 25, 1930 UNITED STATES PATENT OFFICE HEINRICH CLINGESTEIN, OE COLOGNE-ON-THE-RHINE, GERMANY, AND HARRY w. GRIMMEL, OF NEW YORK, N. Y., ASSIG-NORS TO GENERAL ANILINE "WORKS, INC., 01' NEW YORK, N. Y., A CORPORATION OF DELAWARE PRIMARY nmzo DYE DERIVED raoivrnmmno oAnBAzoLEs Ann names or UNSULZPHONATED HYDROXY GARBOXYLIO non) No Drawing. Application filed March' 21', 1927, Serial No. 177,208, and in Germany March 24, 1928.

The present invention I relates to new primary disazo dyestufis derived from diamino carbazoles and arylides of unsulphonated hydroxy carboxylic acids.

5 We have found that exceedingly valuable new azo-dyestufis, insoluble in water, having most probably the general formula wherein R represents the residue of an unsulphonated diamino-carbazole .compound, and R represents an arylide of an 'unsulphonated hydroxy carboxylic acid, are obtained by coupling the tetrazo-compounds of unsulphonated diamino-carbazole compounds with arylides of unsulphonated hydroxy carboxylic acids such as, for example, arylides of 2.3-hydroxy-naphthoic acid, hy-

droxy-naphtho carbazoles, diaceto-acetic acid arylides or the like. a

The new dyestuffs thus obtained are, in the dry state, yellowish-brown to violet to blue to black powders, insoluble in water, soluble in concentrated sulfuric acid to the production of solutions which, for the most part, have a bluish coloration. When produced directly on vegetable fibers, these dyestufis dye very clear yellowish-brown to violet to blue to deep black shades of particular fastness properties; for example, fastness to light and to kier-boiling. properties especially distinguish our dyestuffs from the dyestufis obtained by coupling tetrazotized diamino-carbazole-compounds with- ,B-naphthol, which latter dyestuffs already are known. i

The most valuable of our dyestufi's are 40 those with deep blue to black shades.

These fastness -naphthoic acid-anilide, 15 com. of 34. B.

caustic soda solution and 20 com. of Turkey red oil. It is then well wrung and, without drying, is developed with a solution containing per liter the tetrazo-compound of 5 grams of 2.7 -diamino-carbazole made acid by the, addition of sodium acetate. ing, drying'and soaping the yarn is found to be dyed clear navy blue shades of exceedingly good fastness to kier-boiling and to light. The dyestuff precipitated on the fibre has most probably the formula:

OH OH ble powder which, dissolved in concentrated sulfuric acid, gives a clear blue solution. Upon mixing the sulfuric acid solution with water, blue flakes are produced. In pyridine the dyestufi is soluble with a blue coloration.

By reduction of the dyestufi with stannous chloride and hydrochloric acid, there are The dyestufl is a blue-black water-insolu- After rinsobtained 2.7-diamino-carbazole of the formula:

momma and 1-amin0 2-hydroXy-3-naphthoic acid anilid having the formula:

Ewample 2.1 Vell boiled out and dried cotton yarn is padded with a solution containing per liter 12 grams of 2.3-hydroxy naphthoic acid-alphanaphthalid, 15 ccm. 34 B. caustic soda solution and 20 com. of Turkey red oil. It is then well wrung out and, without drying, is developed with a solution containing per liter the tetrazo-compound from 5 grams of 3.6-dimethyl -2-7 -diam inocarbazole. The

yarn after being further treated in the manner described in Example 1, is found to be dyed clear, deep bluish-black shades of exceedingly good fastness to kier boiling and to li ht.

The dyestuff precipitated on the fibre has most probably the formula:

The dyestuff itself is a black powder, insoluble in water but soluole in concentrated sul furic acid with a bluish coloration. In pyridine it dissolves with a blue coloration. By reduction of the dyestuff with stannous chloride one obtains 2.7 -diamino-3.6-dimethylcarbazole having the formula:

1 NE NH! HRN Etc 7 and CO.NH.C10H1 diamino-carbazole. After rinsing, dr ing and soaping, the yarn is found to be yed a violet shade.

With other diamino-carbazoles as for NH; NH/

NH N=N N=N The dyestuif itself is a bluish-black powder insoluble in water but soluble in concentrated sulfuric acid with a blue coloration. By mixing the sulfuric acid solution with water, reddish-blue flakes are obtained. In pyridine it dissolves With a bluish coloration. By reduction with stannous chloride and hydrochloric acid there are obtained 2.7 -diaminocarbazole and 8-amino-7-hydroxy-2-l-naphtho-carbazole having the formula:

and

NH NH NH: NH

Example 5.The yarn, after being well boiled and dried, is padded with a solution containing per liter 12 grams of diaceto-acetic acid-tolidid, 15 com. of 34 B. caustic soda solution, and 20 com. of Turkey red oil. It is well wrung out and without drying, developed with a solution containing per liter the tetrazo-compound of 5 grams of 2.7 diaminocarbazole made acid by the addition of sodium acetate. After rinsing, drying and soaping the yarn is found to be dyed a strong yellow-brown.

With other diaceto-acetic acid arylids similar colors are obtained. v v

The dyestufi itself is a brownish powder insoluble in Water, but soluble in concentrated sulfuric acid with reddish-blue coloration. In pyridine the dyestufi is soluble with a yellow-brown cploration. The dyestufi has the formula:

CH: CH:

ders, insoluble in water, and soluble in concentrated sulfuric acid to the production of i 5 ontoon=ooown-O-Onnooewon-om i ll H;0.COH=|1J .comuQQ-rzncodhcomom Ha H We claim 1. Processwhich comprises coupling a tet-' razotized unsulphonated diamino-carbazole compound with an arylide of an unsulphonated hydroxy carboxylic acid.

2. Process which comprises coupling a tetrazotized unsulphonated 2.7-diamino-carbazole compound with an arylide of an unsulphonated hydroxy carboxylic acid.

3. Process which comprises coupling a tetrazot-ized unsulphonated 2.7-diamino-carbazole compound with an unsulphonated arylide of 2.3-hydroxy-naphthoic acid.

4. Process which comprises coupling the tetrazo-compound of unsulphonated 3.6- dimethyl-2.7-diamino-carbazole with 2.3- hydroXy-naphthoic acid-alpha-naphthalid.

5. As new products water-insoluble azodyestuffs having the general formula solutions which, for the most part, have a bluish coloration.

7. As new products water-insoluble ,a'zodyestuffs having the general formula wherein R represents the residue of an unsulphonated 2.7 -diamino-carbazole compound and R represents the residue of a 2.3-hydroxy-naphthoic acid arylide which dyestufl's are, in the dry state, yellowish-brown to violet to blue to black powders, insoluble in water, and soluble in concentrated sulfuric acid to the production of sollitions which, for the most part, have a bluish coloration.

8. As a new product a water-insoluble azodyestuif containing the residue of unsulphonated 3.6-dimethyl-2.7-diamino-carbazole and the residue of an unsulphonated 2.3-hydrox-y-naphthoic acid-alpha-naphthalid having most probably the formula:

wherein R represents the residue of an unsulphonated diamino-carbazole compound and R represents the residue of an arylide of an unsulphonatedhydroxy carboxylic acid,which dyestufi's are, in the dry state, yellowishbrown to violet to blue to black powders, in-

soluble in water, and soluble in concentrated sulfuric acid to the production of solutions which, for the most part, have a bluish coloration.

6. As new products water-insoluble azodyestuffs having the general formula wherein R represents the residue of an unsulphonated 2.7 -diamino-carbazolecompound and R represents the residue of an arylide of an unsulphonated hydroxy carboxylic acid, which dyestuffs are, in the dry state, yellowish-brown to violet to blue toblackpowco.NH.cwH1

n "Cer tificateiof Correction Patent No."1', 71',683; 1 GrantedMerch 25; 1930,11;

HEINRICH .CL'INGESTEIN ET AL. I

It is herebj certified that error 'ap'pedrs in theprinred specification of the above numbered patent requiring corre'qtion as follows: Page 2, line 5, in the formula,

for H O read HgN; and that? the said Letters Patent should be read with this correction therein that the 'same may conform to the record. of the case in the Patent Office. I o

Signed and sealed. this 22d day of April, A.'- D. 1930.

-- SEAL.

[ 1 M. J, 'MOORE,

rioting Oom'rm'esioner of Patents. 

